Scattering function and thermodynamics

In addition to the repulsive part of the potential given by Eq. (4), a short-range attraction between the macroions may also be present. This attraction is due to the van der Waals forces [17,18], and can be modelled in different ways. The OCF model can be solved for the macroion-macroion pair-distribution function and thermodynamic properties using various statistical-mechanical theories. One of the most popular is the mean spherical approximation (MSA) [40], The OCF model can be applied to the analysis of small-angle scattering data, where the results are obtained in terms of the macroion-macroion structure factor [35], The same approach can also be applied to thermodynamic properties Kalyuzhnyi and coworkers [41] analyzed Donnan pressure measurements for various globular proteins using a modification of this model which permits the protein molecules to form dimers (see Sec. 7). 

Note that in the hypothetical incompressible limit the form of both the scattering functions and spinodal condition are much simpler than the rigorous expressions of Eqs. (6.4)-(6.6). Although the IRPA can usually be fitted to low wavevector experimental scattering data, and an apparent chi-parameter thereby extracted, the literal use of the IRPA for the calculation of thermodynamic properties and phase stability is generally expected to represent a poor approximation due to the importance of density-fluctuation-induced compressibility or equation-of-state effects [2,65,66]. The latter are non-universal, and are expected to increase in importance as the structural and/or intermolecular potential asymmetries characteristic rrf the blend molecules increase. 

The idealized symmetric blend model is not representative of the behavior of most polymer alloys due to the artificial symmetries invoked. Predictions of spinodal phase boundaries of binary blends of conformationally and interaction potential asymmetric Gaussian thread chains have been worked out by Schwelzer within the R-MMSA and R-MPY/HTA closures and the compressibility route to the thermodynamics. Explicit analytic results can be derived for the species-dependent direct correlation functions > effective chi parameter, small-angle partial collective scattering functions, and spinodal temperature for arbitrary choices of the Yukawa tail potentials. Here we discuss only the spinodal boundary for the simplest Berthelot model of the Umm W t il potentials discussed in Section V. For simplicity, the A and B polymers are taken to have the same degree of polymerization N. 

Note 1 An infinite number of molar-mass averages can in principle be defined, but only a few types of averages are directly accessible experimentally. The most important averages are defined by simple moments of the distribution functions and are obtained by methods applied to systems in thermodynamic equilibrium, such as osmometry, light scattering and sedimentation equilibrium. Hydrodynamic methods, as a rule, yield more complex molar-mass averages. 

There may be many different functional representations of PESs based on a variety of mathematical techniques (e.g. polynomials or splines) and different physical models (e.g. atoms-in-molecule approach). Theoretically, all of them should work adequately in simulations of scattering, spectroscopic or thermodynamic properties. However, we believe... 

Here, (...) = J2pn ri. .. ri) is the appropriate combinedquantal and thermodynamic average (over the classical probabilities pn) related with the condensed matter system. M and n(p) are the mass and momentum distribution of the scattering nucleus, respectively, and ior = q2 /2 M is the recoil energy. For convenience, h = 1. Eq. (2) is of central importance in most NCS experiments, since it relates the SCS directly to the momentum distribution. Furthermore, n(p) is related to the nuclear wave function by Fourier transform and therefore, to the spatial localization of the nucleus. It takes into account the fact that, if the scattering nucleus has a momentum distribution in its ground state, the 5-function centered at uor will be Doppler broadened. 

The thermodynamic properties of block copolymers in disordered state, have been studied by Leibler [1980]. Using the random phase approximation [de Gennes, 1979], the author developed a relation between the segmental density correlation function and the scattering vector. An order parameter, related to the reduced segmental density, was introduced. In the disordered state, this order parameter is zero whereas for the ordered phase, it is a periodic non zero-function. Leibler s demonstrated that the critical condition for microphase separation in di-block copolymers... 

In order to describe the static structure of the amorphous state as well as its temporal fluctuations, correlation functions are introdnced, which specify the manner in which atoms are distributed or the manner in which fluctuations in physical properties are correlated. The correlation fimctions are related to various macroscopic mechanical and thermodynamic properties. The pair correlation function g r) contains information on the thermal density fluctuations, which in turn are governed by the isothermal compressibility k T) and the absolute temperature for an amorphous system in thermodynamic equilibrium. Thus the correlation function g r) relates to the static properties of the density fluctuations. The fluctuations can be separated into an isobaric and an adiabatic component, with respect to a thermodynamic as well as a dynamic point of view. The adiabatic part is due to propagating fluctuations (hypersonic soimd waves) and the isobaric part consists of nonpropagating fluctuations (entropy fluctuations). By using inelastic light scattering it is possible to separate the total fluctuations into these components. 

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